Aromatic polyepoxide treated derivatives of alkylene oxide-amine modified phenolic-resins, and method of making same



* 2,854,432 1C6 Patented Sept. 30, 195

radical, the divalent sulfone radical, and the divalent 2,854,432 monosulfide radical S-, the divalent radical CH SCH and the divalent disulfide radical AROMATIC POLYEPQXIDE IREATED DERIVA' S--S; and R is the divalent radical obtained by TIVES 0F ALKYLENE OXIDE'AMINE MODI' 5 the elimination of a h drox 1 h dro en atom and a nu- FIED PHENULIC RESINS, AND METHOD 0F Y Y Y E M AKING SAME clear hydrogen atom from the phenol Melvin De Groote, St. Louis, and Kwan-Ting Siren, OH

Brentwood, Mo., assignors to Petrolite Corporation, Wilmington, Del., a corporation of Delaware I No Drawing. Original application April 22, 1953, Serial I,

N 350 534 now Patent No. 2 771 433 dated Novem- H, be i' 20, 195%. Divided and tliis a uation June 1s, m whlch R R ,and R representhydro en and hydro- 1956, Serial No. 591,556 carbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms. 4 Claims- A further limited aspect of the invention is represented by the products wherein the oxyalkylated resin condensate is reacted with a member of the class of (a) compounds of the following formula The present invention is a division of our copending application Serial No. 350,534, filed April 22, 1953, now U. S. Patent No. 2,771,433.

Our invention is concerned with new chemical prod- 20 u-cts or compounds useful as demulsifying agents in processes or procedures particularly adapted for prevent- HECQCHTCHPOG ing, breaking or resolving emulsions of the water-in-oil 0 2 p and Particularly Pfiiioieum emilisiohsour ihvenwherein R is essentially an aliphatic hydrocarbon bridge, tion is also concerned with the application of such chemh n independently has one f the values 0 to 1, and ical products or compounds in various other arts and R i an lkyl radical containing from 1 to 4 carbon industries as well as with methods of manufacturing atoms, or even 12 carbon atoms, and (b) cogenericauy the new Chemical Products Compounds which are of associated compounds formed in the preparation of a) outstanding value in demulsification. preceding, including monoepoxides.

Attention is directed to two (lo-Pending De Groom Reference herein to being thermoplastic or non-thermoaPPiiCatiOBS, Serial N41 filed September 1952, setting characterized products as being liquids at ordinary HOW Patent and Serial No. ,3 filed temperature or readily convertible to liquids by merely January w PaiBht 2,771,443- These heating below the point of pyrolysis and thus differeniwO applications described hydrophiie Products Obtained tiates them from infusible resins. Reference to being y the oXyaikyiaiioll oi the condensation Product Of soluble in an organic solvent means any'of the usual iaih Phenol-aldehyde resins with respect to y yi organic solvents, such as alcohols, ketones, esters, ethers, polyamines and formaldehyde. mixed solvents, etc. Reference to solubility is merelyto The Pieseilt invention is concerned with a method of differentiate from a reactant which is not soluble and reacting said oxyalkylated derivatives of the kind just de- 40 might be not only insoluble but also infusible. Furtherscribed with a phenolic polyepoxide of the kind previously more, solubility is a factor insofar that it is sometimes described in our aforementioned co-pending application, desirable to dilute the compound containing the epoxy Serial No. 305,079. 3 rings before reacting with the monoepoxide-derived prod- Thus the Pfesfillt invention is Concerned with Products uct. In such instances, of course, the solvent selected of reaction obtained by a 3s p m n f ng process would have to be one which is not susceptible to oxyalkylinvolving ation, as for example, kerosene, benzene, toluene, dioxndensing certain phenol aldehyderesinmhereinane, various ketones, chlorinate solvents, dibutyl ether, after described in detail, with certain basic hydroxylated dihexyl ether, ethyleneglycol diethylether, diethylenep y hereinafter described in detail, and formaldeglycol diethylcther and dimethoxytetraethyleneglycol. hyde; (2) voxyalkylation of the condensation product with Th expression epoxy is not usually limited to the certain monoepoxides, hereinafter described in detail; 1,2-epoxy ring. The 1,2-epoxy ring is sometimes reand (3) oxyalkylation of the previously oxyalkylated ferred to as the oxirane ring to distinguish it from other resin condensate with certain phenolic polyepoxides, hereepoxy rings. Hereinafter the word epoxy unless indiinafter described in detail, and cogenerically associated cated otherwise, Will be used to mean the oxirane ring, compounds formed in their preparation. i. e., the 1,2-epoxy ring. Furthermore, where a com- A more limited aspect of the present invention is conpound has two or more oxirane rings they will be referred cerned with products of reaction wherein the oxyalkylto as polyepoxides. They usually represent, of course, ated resin condensate is reacted with a member of the 1,2-epoxy rings or oxirane rings in the alpha-omega class of compounds of the following formula: position. This is a departure, of course, from the stand- 0 H o C O-0-[ORi[R],.-RiOCC]OR [R],.-R1O--CC G H2 H Hz Ha I H: H: H H,

OH in which R represents a divalent radical including ketone point of strictly formal nomenclature as in the example residues formed by the elimination of the ketonic oxygen of the simplest diepoxide which contains at least 4 caratom and aldehyde residues obtained by the elimination bon atoms and is formally described as l,2-epoxy-3,4- of the aldehydic oxygen atom; the divalent radical b uggfl diepoxybutane). H E It well may be that even though the previously suggested formula represents the principal component, or the divalent components, of the resultant or reaction product dei scribed in the previous text, it may be important to note that somewhat similar compounds, generally of much higher molecular weight, have been described as complex resinous epoxides which are polyether derivatives of polyhydric phenols containing an average of morethan one epoxide group per molecule and free from functional groups other than epoxide and hydroxyl groups. See U. S. Patent No. 2,494,295, dated January 10, 1950, to Greenlee. The compounds here included are limited to the monomers or. the low molal members of such series and generally contain two epoxide rings per molecule and may be entirely free from a hydroxyl group. This is important because theinstant invention is directed towards products which are not insoluble resins and have certain solubility characteristics not inherent in the usual thermosetting resins. I

, Having obtained a reactant having generally 2 epoxy rings as depicted in the last formula preceding, or low molal polymers thereof, it becomes obvious the reaction can'take place with any oxyalkylated phenol-aldehyde resin by virtue of the fact that there are always present either phenolic hydroxyl radicals or alkanol radicals resulting fromitheoxyalkylation of the phenolic hydroxyl radicals; there may be present reactive hydrogen atoms attached to a'nitrogen atom or an oxygen atom, depending on whether initially there was present a hydroxylated group attached to an amino hydrogen group or a secondaryv amino group. In any event there is always a multiplicity of reative hydrogen atoms present in the oxyalkylated amine-modified phenol-aldehyde resin.

To illustrate the products which represent the subject matter of the present invention reference will be made to a reaction involving a mole of the oxyalkylating agent, i. e., the compound having two oxirane rings and an oxyalkylated amine condensate. Proceeding with the example previously described it is obvious the reaction ratio of two moles of the oxaylkylated amine condensate to one mole of the oxyalkylating agent gives a product which may be indicated as follows: I

4 alkylation proceeds the significance of the basicity of any nitrogen group is obviously diminished.

The polyepoxide-treated condensates obtained in the manner described are, in turn, oxyalkylation-susceptible and valuable derivatives 'can'be obtained by further reaction with ethylene oxide, propylene oxide, ethylene imine, etc.

Similarly, the polyepoxide-derived compounds can be reacted with a product having both a nitrogen group and a 1,2-epoxy group, such as 3-dialkylaminoepoxypropane. See U. S. Patent No. 2,520,093, dated August 22, 1950, to Gross.

Although the herein described products have a number of industrial applications, they are of particular value for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cutoil, roily' oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring Waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

The new products are useful as wetting, detergent and leveling agents in the laundry, textile and dyeing industries; as wetting agents and detergents in the acid washing of building stone and brick; as wettingagents and spreaders in the application of asphalt in road building and the like; as a flotation reagent in the flotation separation of various aqueous suspensions containing negatively charged particles, such as sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides, emulsifying agents, as, for example for cosmetics, spray oils, water-repellent textile finishes; as lubricants, etc.

in which the various characters have their previous significance and the characterization oxyalkylated condensate? is simply anabbreviation for the oxyalkylated condensate which is described in greater detail subsequently. I

Such final product in turn also must be soluble but solubility is not limited to an organic solvent but may in cludefwatenor for that matter, a solution of water containing an acid such as hydrochloric acid, acetic acid, hydroxyacetic acid, etc. In other words, the nitrogen groups present, whether two or more, may or may not be significantly basic and it is immaterial whether aqueous compounds have distinct water-solubility or are distinctly dispcrsible in 5% gluconic acid. For instance, the products freed from any solvent can be shaken with S to .20 times their weight of 5% gluconic acid at ordinary temperature and showat least some tendency towards being self-dispersing. The solvent which is generally tried is xylene. If xylene alone does not serve then a mixture of xylene and methanol, for instance, 80 parts of xylene and 20 parts of methanol, or parts of xylene and 30 parts of methanol, can be used. Sometimes it is desirable to adda small amount of acetone to the xylene-methanol mixture, for instance, 5% to 10% of acetone. As oxyare not xylene-soluble the obvious chemical equivalent or equivalent chemical test canbe made by simply using.

some suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will.be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of the xylene in the emulsification test includes such obvious variant. 7 For purpose of convenience, what is said hereinafter will be divided into ten parts with Part 3, in turn, being divided into three subdivisions:

Part 1 is concernedwith our preference in regard to the polyepoxide and particularly the diepoxide reactant;

Part 2 is concerned with certain theoretical aspects of diepoxide preparation;

Part 3, Subdivision A, is concerned with the preparation of monomeric diepoxides, including Table I;

Part 3, Subdivision B, is concerned with the prepara- Ff, a

tion of low molal polymeric epoxides or mixtures containing low molal polymeric epoxides as well as the monomer and includes Table II;

Part 3, Subdivision C, is concerned with miscellaneous phenolic reactants suitable for diepoxide preparation;

Part 4 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction to yield an amine-modified resin;

Part 5 is concerned with appropriate basic hydroxylated polyamines which may be employed in the preparation of the herein-described amine-modified resins;

Part 6 is concerned with reactions involving the resin, the amine, and formaldehyde to produce specific products or compounds which are then subjected to oxyalkylation with monoepoxides;

Part 7 is concerned with the oxyalkylation of the products described in Part 6, preceding;

Part 8 is concerned with reactions involving the two preceding types of materials and examples obtained by such reactions. Generally speaking, this involves nothing more than a reaction between two moles of a previously prepared oxyalkylated amine-modified phenol-aldehyde resin condensate as described and one mole of a polyepoxide so as to yield a new and larger resin molecule or comparable product;

Part 9 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products; and

Part 10 is concerned with uses for the products herein described either as such or after modification, including any applications other than those involving resolution of petroleum emulsions of the water-in-oil type.

PART 1 As will be pointed out subsequently, the preparation of polyepoxides may include the formation of a small amount of material having more than two epoxide groups per molecule. If such compounds are formed they are perfectly suitable except to the extent they may tend to produce ultimate reaction products which are not solventsoluble liquids or low-melting solids. Indeed, they tend to form thermosetting resins or insoluble materials. Thus, the specific objective by and large is to produce diepoxides as free as possible from any monoepoxides and as free as possible from polyepoxides in which there are more than two epoxide groups per molecule. Thus, for practical purposes what is said hereinafter is largely limited to polyepoxides in the form of diepoxides.

As has been pointed out previously one of the reactants employed is a diepoxide reactant. It is generally obtained from phenol (hydroxybenzene) or substituted phenol. The ordinary or conventional manufacture of the epoxides usually results in the formation of a cogeneric mixture as explained subsequently. Preparation of the monomer or separation of the monomer from the remaining mass of the co-generic mixture is usually expensive. If monomers were available commercially at a low cost, or if they could be prepared without added expense for separation, our preference would be to use the monomer. Certain monomers have been prepared and described in the literature and will be referred to subsequently. However, from a practical standpoint one must weigh the advantage, if any, that the monomer has over other low molal polymers from a cost standpoint; thus, we have found that one might as well attempt to prepare a monomer and fully recognize that there may be present, and probably invariably are present, other low molal polymers in comparatively small amounts. Thus, the materials which are most apt to be used for practical reasons are either monomers with some small amounts of polymers present or mixtures which have a substantial amount of polymers present. Indeed, the mixture can be prepared free from monomers and still be satisfactory. Briefly, then, our preference is touse 5 the monomer or the monomer with the minimum amount of higher polymers.

It has been pointed out previously that the phenolic nuclei in the epoxide reactant may be directly united, or united through a variety of divalent radicals. Actually, it is our preference to use those which are commercially available and for most practical purposes it means instances where the phenolic nuclei are either united directly without any intervening linking radical, or else united by a ketone residue or formaldehyde residue. The commercial bis-phenols available now in the open market illustrate one class. The diphenyl derivatives illustrate a second class, and the materials obtained by reacting substituted monofuctional phenols with an aldehyde illustrate the third class. All the various known classes may he used but our preference rests with these classes due to their availability and ease of preparation, and also due to the fact that the cost is lower than in other examples.

Although the diepoxide reactants can be produced 'n more than one way, as pointed out elsewhere, our preference is to produce them by means of the epichlorohydrin reaction referred to in detail subsequently.

One epoxide which can be purchased in the open market and contains only a modest amount of polymers corresponds to the derivative of bis-phenol A. It can be used as such, or the monomer can be separated by an added step which involves additional expense. This compound of the following structure is preferred as the epoxide reactant and will be used for illustration repeatedly with the full understanding that any of the other epoxides described are equally satisfactory, or that the higher polymers are satisfactory, or that mixtures of the monomer and higher polymers are satisfactory. The formula for this compound is CH3 H H H l H H W ?C Reference has just been made to bis-phenol A and a suitable epoxide derived therefrom. Bis-phenol A is dihydroxy-diphenyl-dimethyl methane, with the 4,4 isomers predominating and with lesser quantities of the 2,2 and 4,2 isomers being present. It is immaterial which one of these isomers is used and the commercially available mixture is entirely satisfactory.

Attention is again directed to the fact that in the instant part, to Wit, Part 1, and in succeeding parts, the text is concerned almost entirely with epoxides in which there is no bridging radical or the bridging radical is derived from an aldehyde or a ketone. It would be immaterial if the divalent linking radical would be derived from the other groups illustrated for the reason that nothing more than mere substitution of one compound for the other would be required. Thus, what is said hereinafter, although directed to one class or a few classes, applies with equal force and effect to the other classes of epoxide reactants.

If sulfur-containing compounds are prepared they should be freed from impurities with considerable care for the reason that any time that a low-molal sulfur-containing compound can react with epichlorohydrin there may be formed a by-product in which the chlorine happened to be particularly reactive and may represent a product, or a mixture of products, which would be unusually toxic, even though in comparatively small concentration.

be derived by more than one method as, for example, the use of epichlorohydrin or glycerol dichlorohydrin. A

number of problems are involved in attempting to produce these materials free from cogenericrnaterials of related composition. For aydiscussion of thesedifliculties,

reference is made to U. S. Patent No. 2,819,212, beginning at column 7, line 21.

included for purpose of illustration.

scrihe i n h we paten s J t 1 m wmpounds l a d These P i ular m ample Diphenol Digl'yeidyl ether munumber A enee Di(epoxypropoxyphenyl methane.. 2,506,486 Di(epoxypropoxyphenyl methylmethane 2,506,486 Di(epoxypropoxyphenyl dlmethylmethme.-. f 2,506,486 Di(epoxypropoxyphenylethylmethylmethan 2, 506, 486 Di(epoxypropoxyphenyl diethylmethane 2, 500,486 Di (epoxypropoxyphenyl) methylpropylmethane 2, 500, 486 Di(epoxypropoxyphenylgmethylphenylmethane 2, 600, 486 Di(epoxypropoxypheny1 ethylphenylamethane. ;-2,'500, 486 Di(epoxypropoxyphenybgropfl hen 'lmethane 2,506,486 Di(epoxypropoxyphenyl) at p eny 2,506,486 114... (CHSCnHi)CH(G5H40H)2. Di(epoxyp'r qpoxyphe nyl) toly methane". 2,500,486 1214"..- (CH3C5H4)G(OHI) (CoH4OH)z...- Di(epoxypropoxyphenymolylmethylm 2,506, 486 13A"... Dihydroxy diphenyl 4,4-his(2,3Fepoxypropoxy)diphonyl 2,531,353 14A (CH3)G(C4H5.O.H3OH)1 2,Z-bis(4 (2,3 eporypropoxyfl-tertiarybutyl ph 2,530,353

PART 3 ,zSllbdlW-HOII B.

Subdivision A The preparations of the diepoxy derivatives of the diphenols, which are sometimes referred to as diglycidyl ethers, have been described in a number of patents. For convenience, reference will be made to two only, to wit, aforementioned U. S. Patent 2,506,486, and aforementioned U. S. Patent No. 2,530,353.

As to the preparation of low-molal polymeric epoxid'es ormixtures reference is made toaforementionedfUi S. Eatents Nos. 2,575,558 and 2,582,985. In light of U. S. Patent No. 2,575,558, the following 30 examples can be specified by reference to theformula therein provided one still lbears over-simplification.

TABLE II inm ind it is in essence an (in which the characters have their previous significance) Example R10ir0m HRiOH -nn Remarks number B1 Hydroxy' benzene; CH: 0,1,2 Phenol known as biahenoi A. Low polymeric mixture is ut or meme where n=0, remainder largely when A n'=1, some where a'=2. H: r

3a.. -.----ao on. 0,1,2 Phenolknownesbis-phenolh. samba 1 2; regarding B1 ebove. 1.; 41H] n. B3 Orthobutylphenol 0H. 0,1,2 Even though 1: is preiereblg 0, min. usual reaction product in t well contain materials where n 1. or to, e

5 leeaerdegree 2.

134 Orthoemyiphenol ((IJJH; 0,1,2 Do.

B6 Orthooctylphenol in. 0,1,2 Do.

B6 Orthononylphenol. ZR: 0,1,2 Do.

B7 Orthododeoylphenol 31h 0,1,2 Do.

in. r

B8 Metecresol CH; 0,1,2 Bee prior note. This phenol u initial material is known as bis-phenol C. For other suitable bis-phenols see m' U. 8. Patent 2,564,191.

TABLE 11 (continued) Example R!O from HRIOH R n n Remarks number B9 Metacresol EH; 1 0,1,2 See prior note.

B Dibutyl (ortho-paralphenolv 1 0,1,2 D0.

B11 Diamyl (ortho-para) phenol. 13 1 0, 1, 2 Do.

B12 Dioetyl (ortho-para) phenoL 1% 1 0,1,2 Do.

B13.. Dinonyl (ortho-para) phenol. 1g 1 0,1,2 Do.

B14 Diamy1(ortho-para) phenol. El 1 0,1,2 Do.

B15 do H 1 0,1,2 Do.

CgHu- B16 Hydroxy benzene (I) 1 0,1,2 Do.

B17. Diamyl phenol (ortho-para)- SS- 1 0,1,2 Do. B18.. r..do s- 1 0,1,2 Do. B19 Dibutyl phenol (ortho-para)' 13 g 1 0,1,2 D0.

B20 do H H 1 0,1,2 Do.

. C C H H 1321 Dinonylphenol(ortho-para) lg 161 1 0,1,2 Do.

322...-.. Hydroxy benzene (I? 1 0,1,2 Do.

B23 do Nonew, 0 0,1,2 Do. B24 Ortho-isopropyl phenol CH: 1 0,1,2 See prior note. As to preparation of4,4- l lsopropylidene bis-(2-isopropylphenol) C see U. S. Patent No. 2,482,748, dated I Sept. 27, 1949, to Dietzler. CH3

B25 Para-octyl phenol -CHz-SCH1 1 0,1,2 See prior note. (As to preparation of the phenol sulfide see U. S. Patent No. 2,488,134, dated Nov. 15, 1949, Mikeska et a1.)

1326 Eydroxybenzene CH: 1 0,1,2 See prior note. (As to preparationofthe 1 phenol sulfide see U. S. Patent No. (|J 2,526,545.)

F .i, C,H,

Subdivision C as in the instance of cyclohexylphenol or phenylphenol. Th 1 h b d 1 h Such substituents are usually in the ortho position and QP F P ave F argey to t Ose may be illustrated by a phenol of the following comm which there is no divalent linking radlcahas 1n the case position: of diphenyl compounds, or where the linking radical is derived from a ketone or aldehyde, particularly a ketone. Needless to say, the same procedure is employed in converting diphenyl into a diglycidyl ether regardless of the CH3 nature of the bond between the two phenolic nuclei. For purpose of illustration attention is directed to numerous other diphenols which can be readily converted to a suitable polyepoxide, and particularly diepoxide, reactant.

As previously pointed vout the initial phenol may be substituted, and the substituent group in turn may be a y 7 Similar phenols which are monofunctional, for instance,

gyclic group such as the phenyl group or cycloheXyl group paraphenyl phenol or paracyclohexyl phenol with an additional substituent in the ortho position, maybe employed in reactions previously referred. to, for instance,

.with formaldehyde or sulfur chlorides to give comparable phenolic compounds having 2 hydroxyls and suitable for 5 subsequent reaction with epichlorohydrin, etc.

Other samples include:

OH H OH R U RI i Ks HI wherein R, is a substituent selected from the class consisting of secondary butyl and tertiary butyl groups and R, is a substituent selected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groupsyand wherein said alkyl group contains at least 3 carbon atoms. See U. S. Patent No. 2,515,907.

in which the -C,H groups are secondary amyl groups. See U. S. Patent No. 2,504,064.

wherein R is a member of the group consisting-of-alkyl, and alkoxyalkyl radicals containing from 1 to 5 carbon atoms, inclusive, and aryl and chloraryl radicals of the benzene series. See U. S. Patent No. 2,526,545.

on on s5 wherein R is a substituent selected from the class consisting of secondary butyl and tertiary butyl groups and R, is a substituent selected from the class consisting of alkyl,

vention:

cycloallryl, aryl, aralkyl, and alkaryl groups. See U. S.

Patent No. 2,515,906.

CE=CH oa c J: i

Etc-61:211. mc-gglom T,

See U. S. Patent No. 2,515,908.

As to sulfides, the following compound is of interest:

ClHu CsHn Q See U. S. Patent No. 2,331,448.

As to descriptions of various suitable phenol sulfides, reference is made to the following patents: U. S. Patent: Nos. 2,246,321, 2,207,719, 2,174,248, 2,139,766, 2,244,- 021, and 2,195,539.

As to sulfones, see U. S. Patent No. 2,122,958.

As to suitable compounds obtained by the use of formaldehyde or some other aldehyde, particularly compounds such as H H O O Alkyl Alkyl Alkyl Alkyl in which R, is a methylene radical, or a substituted methylene radical which represents the residue of an aldehyde and is preferably the unsubstituted methylene radicalde rived from formaldehyde. See U. S. Patent No. 2,430,002.

See also U. S. Patent No. 2,581,919 which describes di(dialkyl cresol),sulfides which include the monosulfidcs, the disulfides, and the polysulfides. The following formula represents the various dicresol sulfides of this inon em cm 011 Rs R1 R1 RI in which R, and R, are alkyl groups, the sum of whose carbon atoms equals 6 to about 20, and R, and R, each preferably contain 3 to about 10 carbon atoms, and x is l to 4. The term sulfides" as used in'this text, therefore, includes monosulfide, disulfide, and polysulfides.

PART 4 It is well known that one can readily purchase on the open market, or prepare, fusible, organic solvent-soluble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula In the above formula 1: represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably 10 orl2 units, particularly when the resin is subjected to 13 I4 heating under a vacuum as described in the literature. A In conducting reactions of this kind one does not neclimited sub-genus is in the instance of low molecular essarily obtain a hundred percent yield for obvious rea- Weight polymers where the total number of phenol nuclei sons. Certain side reactions may take place. For invaries from 3 to 6, i. e., n varies from 1 to 4; R represents stance, 2 moles of amine may combine with one mole an aliphatic hydrocarbon substituent, generally an alkyl 5 of the aldehyde, or only one mole of the amine may comradical having from 4 to 15 carbon atoms, such as butyl, bine with the resin molecule, or even to a very slight amyl, hexyl, decyl or dodecyl radical. Where the divalent extent, if at all, 2 resin units may combine without any bridge radical is shown as being derived from formaldeamine in the reaction product, as indicated in the followhyde it may, of course, be derived from any other reactive ing formulas: aldehyde having 8 carbon atoms or less. 10

Because a resin is organic solvent-soluble does not mean R1 R1 it is necessarily soluble in any organic solvent. This is H 1 N-C-N particularly true where the resins are derived from trt- H functional phenols as previously noted. However, even R1 R1 when obtained from a difunctional phenol, for instance,

paraphenylphenol, one may 0 tain a resin which is not OH OH OH soluble in a nonoxygenated solvent, such as benzene, or H r H xylene, but requires an oxygenated solvent such as a low g* H g molal alcohol, dioxane, or diethyleneglycol diethylether.

Sometimes a mixture of the two solvents (oxygenated and nonoxygenated) will serve. See Example 9a of U. S. I R R 3 Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser. The resins herein employed as raw materials must be OH H I OH 1 OH H OH H OH 1 OH soluble in a nonoxygenated solvent, such as benzene or C O O- 0 0- xylene. This presents no problem insofar that all that is H H H H required is to make a solubility test on commercially available resins, or else prepare resins which are xylene R R R R or benzene-soluble as described in aforementioned U. S.

Patent No. 2,499,365, or in U. S. Patent No. 2,499,368,

dated March 7, 1950, to De Groote and Keiser. In said patent there are described oxyalkylation-susceptible, fusible, nonoxygenated-organic solvent-soluble, water-insoluble, low-stage phenolaldehyde resins having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule. These resins are 011 OH '1 OH difunctional only in regard to methylol-forming reactivity, .O O

R R n R As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

are derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol, and are formed in the substantial absence of trifunctional phenols. The phenol is of the formula in which R" is the divalent radical obtained from the particular aldehyde employed to form the resin. For rea- OH sons which are obvious the condensation product obtained appears to be described best in terms of the method of R manufacture.

As previously stated the preparation of resins, the kind herein employed as reactants, is well known. See previously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. 0 In other words, if prepared by using a strong acid as a with two moles of formaldehyde and two moles of a basic cata'lyst Such Strong @Icid ld be neutralized. Similarhydroxylated secondary amine as specified, following the 3 If Stmng base 15 used as a catalyst 1S Preferable same idealized over-simplification previously referred to, that the 9 be neutrallmd althqugh We have found the resultant moduct might b6 illustrated thus: that sometimes the reaction described proceeded more 60 rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent and as much as a few 10ths of a percent. Sometimes in which R is an aliphatic hydrocarbon radical having at least 4 carbon atoms and not more than 24 carbon atoms, and substituted in the 2,4,6 position.

If one selected a resin of the kind just described previously and reacted approximately one mole of the resin 1' 0H 0H OH R H H 13 H moderate increase in caustic soda and caustic potash may NC- c-- 0- -O-H H H H H be used. However, the most desirable procedure in prac tically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, R n R i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some The basic hydroxylated amine may be designed thus: 7 trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins we found no reason for using other than those which are lowest in price and most readily available commercially. For pur 15 poseof conveniencesuitable resins are characterized in the following table:

TABLE 111 Mo]. wt. of resin molecule Position of R (based 7 on n+2) cnOvmmcnQucn menu or Tertiary butyl- 882.

Secondary butyl Tertiary amyl Mixed secondary and tertiary amyl. ro

D yl Tertiary butyl d Tertiary amyl Non thl- O O i U! DIOIUI Tertiary butyl Tertiary amyl. Non Tertiary butyL Tertiary amyL. Nonyl HOAO MO a es: ea

PART 5 As has beenpointed out, the amine herein employed as a reactant is a hydroxylated basic polyamine and preferably a strongly basic polyamine having at least one secondary amino radical, free from primary amino groups, free from substituted imidazoline groups, and free from substituted tetrahydropyrimidine groups, in which the hydrocarbon radicals present, whether monovalent or divalent are alkyl, alkycyclic, arylalkyl, or heterocyclic in character, subject of course to the inclusion ofv a hydroxyl group attached to a carbon atom which in turn is part of a monovalent or divalent radical.

Previous reference has been made to a number of polyamines which are satisfactory for use as reactants in the instant condensation procedure. They can be obtained by hydroxylation of low cost polyamines. The cheapest amines available are polyethylene amines and polypropylene amines. In the case of the polyethylene amines there may be as many as 5, 6 or 7 nitrogen atoms. Such amines are susceptible to terminal alkylation or the equivalent, i. e., reactions which convert the terminal primary amino group or groups into a secondary or tertiary amine radical. In the ease of polyamincs having at least 3 nitrogen atoms or more, both terminal groups could be converted into tertiary groups, or'one terminal group could be converted into a tertiary group and the other into a secondary amine group. In the same way, the polyamines can be subjected to hydroxyalkylation by reaction with ethylene oxide, propylene oxide, glycide, etc. In some instances, depending on the structure, both types of reaction may be employed, i. e., one type to introduce a hydroxy ethyl group, for example, and another type to introduce a methyl or ethyl radical.

By way of example the following formulas are ineluded. It will be noted they include such polyamines 16 which, instead of being obtained from ethylene dichloride, propylene dichloride, or the like, are obtained from dichloroethyl others in which the divalent radical has a carbon atom chain interrupted by an oxygen atom:

Room. on.

E N-propylene-N-propylene-N NCIHNCIHINOIHN CIHIN H H H CH1 C I Another procedure for producing suitable polyamines is a reaction involving first an alkylene imine, such as ethylene imine or propylene imine, followed by an alkylene oxide, such as ethylene oxide, propylene oxide or glycide.

What has been said previously may be illustrated by reactions involving a secondary alkyl amine, or a secondary alicyclic amine, such as dibutylamine, dibenzylamine, dieyclohexylamine, or mixed amines with an imine so as to introduce a primary amino group which can be reacted with an alkylene oxide followed by reaction with an imine and then the use of an alkylene oxide again. Similarly, one can start with a primary amine and introduce two moles of an alkylene oxide so as to have a compound comparable to ethyl diethanolamine and react with two moles of an imine and then with two moles of ethylene oxide.

Reactions involving the same reactants previously described, i. e., a suitable secondary monoamine plus an alkylene imine plus an alkylene oxide, or a suitable monoamine plus an alkylene oxide plus an alkylene imine and plus the second introduction of an alkylene oxide, can be applied to a variety of primary amines. In the ease of primary amines one can either employ two moles of an alkylene oxide so as to convert both amino hydrogen atoms into an alkanol group, or the equivalent; or else the primary amine can be converted into a-sccondary amine by the alkylation reaction. In any event, one can obtain a series of pr'imary amines and corresponding secondary amines which are' characterized by the fact that such amines include groups having repetitious ether linkages and thus introduce a definite hydrophile effect by virtue of the ether linkage. Suitable polyether amines susceptible to conversion in the manner described include GIHIOH those of the formula in which X is a small whole number having a value of 1 or more, and may be as much as 10 or 12; n is an integer having a value of 2 to 4, inclusive; m represents the numeral 1 to 2; and m represents a number to 1, with the proviso that the sum of in plus m equals 2; and R has its prior significance, particularly as a hydrocarbon radical.

The preparation of such amines has been described in the literature and particularly in two United States patents, to wit, U. S. Nos. 2,325,514, dated July 27, 1943, to Hester, and 2,355,337, dated August 8, 1944, to Spence. The latter patent describes typical haloalkyl ethers such as CHg-CH1 Cg: CHE-CHzO 0311 002114131 Ciz sO 02 40 C2 40 021140 0 11,01

Such haloalkyl ethers can react with ammonia, or with a primary amine such as methylamine, ethylamine, cyclohexylamine, etc., to produce a secondary amine of the kind above described, in which one of the groups attached to nitrogen is typified by R. Such haloalkyl ethers also can be reacted with ammonia to give secondary amines as described in the first of the two patents mentioned immediately preceding. Monoamines so obtained and suitable for conversion into appropriate polyamines are exemplified ZNH.

Other similar secondary monoamines equally suitable for such conversion reactions in order to yield appropiate secondary amines, are those of the composition as described in U. S. Patent No. 2,375,659, dated May 8, 1945, to Jones et al. In the above formula R may be methyl, ethyl, propyl, amyl, octyl, etc.

Other suitable secondary amines which can be converted into appropriate polyamines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylamine or the alkylation of similar primary amines, or for that matter, amines of the kind described in U. S. Patent No. 2,482,546, dated September 20, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following: beta-phenoxyethylamine, gamma-phenoxypropylamine, beta-phenoxy-alpha-methylethylamine, and beta-phenoxypropylamine.

Other secondary monoamines suitable for conversion into polyamines are the kind described by British Patent No. 456,517, and may be illustrated by In light of the various examples of polyamines which have been used for illustration it may be well to refer again to the fact that previously the amine was shown as with the statement that such representation is an oversimplification. It was pointed out that at least one 18 occurrence of R must include a secondary amino radical of the kind specified. Actually, if the polyamine radical contains two or more secondary amino groups the amine may be reactive at two dilierent positions and thus the same amine may yield compounds in which R and R are dissimilar.

C Hs\ H /N propyleneNpropyleneN H CH5 CH5 In the first of the two above formulas if the reaction involves a terminal amino hydrogen obviously the radicals attached to the nitrogen atom, which in turn combines with the methylene bridge, would be different than if the reaction took place at the intermediate secondary amino radical as differentiated from the terminal group. Again, referring to the second formula above, although a terminal amino radical is not involved it is obvious again that one could obtain two different structures for the radicals attached to the nitrogen atom united to the methylene bridge, depending on whether the reaction took place at either one of the two outersecondary amino groups, or at the central secondary amino group. If there are two points'of reactivity towards formaldehyde as illustrated by the above examples it is obvious that one might get a mixture in which in part the reaction took place at one point and in part at another point. Indeed, there are well known suitable polyamine reactions where a large variety of compounds might be obtained due to such multiplicity of reactive radicals. This can be illustrated by the following formula:

Certain hydroxylated polyamines which may be employed and which illustrate the appropriate type of reactant used for the instant condensation reaction may be illustrated by the following additional examples:

HO CHzCHzNH-OHzCHr-NHCHzCHzOH HOCHaCHaNH-CHr HOCHsCHzNH- H HOCHzOHzNH- z CHaNHCH: CH NHCHr-COHzOH CHaNHOHa GET-CHI CHi-CHI HO-0E HO-NH-OHsCHz-NH-O no-orr CHr-Cfiz orn cr n As is well known one can prepare ether amino alcohols of the type ROCH CH OH) CH NHCH CH NHCH CH (OH) CHg-OR in which R represents an alkyl group varying from methyl to normal decyl, and in fact, the group may contain as many as 15, 20 or even 30 carbon atoms. See J. Org. Chem., 17, 2 (1952).

Over and above the specific examples which have appeared previously, attention is directed to the fact that a number of suitable amines are included in subsequent Table IV.

PART 6 The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is difficult to actually depict the final product of the cogeneric mixture except in terms of the process itself Previous reference has been made to the fact that the procedure herein employed is comparable, in a general way, to that which corresponds to somewhat similar derivatives made either from phenols as differentiated from a resin, or in the manufacture of a phenol-aminealdehyde resin; or else from a particularly selected resin and an amine and formaldehyde in the manner described in Bruson Patent No. 2,031,557 in order to obtain a heat-reactive resin. Since the condensation products obtained are not heat-convertible and since manufacture is not restricted to a single phase system, and since temperatures up to C. or thereabouts may be employed, it is obvious that the procedure becomes comparatively simple. Indeed, perhaps no description is necessary over and above what has been said previously, in light of subsequent examples. However, for purpose of clarity the following details are included.

A convenient piece of equipment for preparation of these cogeneric mixtures is a resin pot of the kind described in aforementioned U. S. Patent No. 2,499,368.

In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction it employed as subsequently described; in fact, usually, it is apt to be a solid at distinctly higher temperatures, for instance, ordinary room temperature. Thus, we have found it convenient to use a solvent and particularly one which can be removed readily at a comparatively moderate temperature, for instance, at 150 C. A suitable solvent is usually benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such or similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction,

takes place in a polyphase system. However, if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively non-volatile solvent such as dioxane or the diethylether of ethyleneglycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necessary to use an initial resin which is soluble only in any oxygenated solvent as just noted, and it is not necessary to have a single phase system for reaction.

Actually, water is apt to be present as a solvent for the reason that in most cases aqueous formaldehyde is employed, which may be the commercial product which is approximately 37%, or it may be diluted down to about 30% formaldehyde. However, paraformaldehyde can'be used but it is more diflicult perhaps to add a solid material instead of the liquid solution and, everything else -being equal, the latter is apt to be more economical. In any event, water is present as water of reaction. If the solvent is completely removed at the end of the process, no problem is involved if the material is used for any subsequent reaction. However, if the reaction mass is going to be subjected to some further reaction where the solvent may be objectionable, as in the case of ethyl or hexyl alcohol, and if there is to be subsequent oxyalkylation, then, obviously, the alcohol should not be used or else it should be removed. The fact that an oxygenated solvent need not be employed, of course, is an advantage for reasons stated.

The products obtained, depending on the reactants selected, may be water-insoluble or water-dispersible, or water-soluble, or close to being water-soluble. Water solubility is enhanced, of course, by making a solution in the acidified vehicle such as a dilute solution, for instance, a 5% solution of hydrochloric acid, acetic acid, hydroxyacetic acid, etc. One also may convert the finished product into salts by simply adding a stoichiometric amount of any selected acid' and removing any water present by refluxing with benzene or the like. In fact, the selection of the solvent employed may depend in part whether or not the product at the completion of the reaction is to be converted into a salt form.

We have found no particular advantage in using a low temperature in the early stage of the reaction because, and for reasons explained, this is not necessary although it does apply in some other procedures that, in a general way, bear some similarity to the present procedure. There is no objection, of course, to giving the reaction an opportunity to proceed as far as it will at some low temperature, for instance, 30 to 40 but ultimately one must employ the higher temperature in order to obtain products of the kind herein described. If a lower temperature reaction is used initially the period is not critical, in fact, it may be anything from a few hours up to 24 hours. We have not found any case where it Was necessary or even desirable to hold the low temperature stage for more than 24 hours. In fact, we are not convinced there is any advantage in holding it at this stage for more than 3 or 4 hours at the most. This, again, is a matter of convenience largely for one reason. In heating and stirring the reaction mass there is a tendency for formaldehyde to be lost. Thus, if the reaction can be conducted at a lower temperature so as to use up part of the formaldehyde at such lower temperature, then the amount of unreacted formaldehyde is decreased subsequently and makes it easier to prevent any loss. Here, again, this lower temperature is not necessary by virtue of heat convertibility as previously referred to.

If solvents and reactants are selected so that the reactants and products of reaction are mutually soluble, then agitation is required only to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is not necessary as previously pointed out but may be convenient under certain circumstances. On the other hand, if the products are not mutually soluble then agitation should be more vigorous for the reason that reaction probably takes place principally at the interfaces and the more vigorous the agitation the more interfacial area. The general procedure employed is invariably the same when adding the resin and the selected solvent, such as 'benzene or xylene. Refluxing should be long enough to insure that the resin added,.preferably in a powdered form, is completely dissolved. However, if the resin is prepared as such it may be added in solution form, just as prepara-' tion is described in aforementioned U. S. Patent 2,499,368. After the resin is in complete solution the polyamine is added and stirred. Depending on the polyamine selected, it may or may not be soluble in the resin solution. If it is not soluble in the resin solution it may be soluble in the aqueous formaldehyde solution. If so, the resin then will dissolve in the formaldehyde solution as added, and if not, it is even'possible that the initial reaction mass could be a three-phase system instead of a two-phase system although this would be extremely unusual. This solution, or mechanical mixture, if not completely soluble is cooled to at least the reaction temperature or somewhat below, for example 35 C. or slightly lower, provided this initial low temperature stage is employed. The formaldehyde is then added in a suitable form. For reasons pointed out we prefer to use a solution and whether to use a commercial 37% concentration is simply a matter of choice. In large scale manufacturing there may be some advantage in using a 30% solution of formaldehyde but apparently this is not true on a small laboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it easier to control unreacted formaldehyde loss.

hyde loss control, one can use a more dilute form of On a large scale if there is any difliculty with formalde- I 7. 22 formaldehyde, for instance, a 30% solution. The reaction can be conducted in an autoclave and no attempt made to remove water until the reaction is over. Generally speaking, such a procedure is much less satisfactory for a number of reasons. For example, the reaction does not seem to go to completion, foaming takes place, and other mechanical or chemical difficulties are involved. We have found no advantage in using solid formaldehyde because even here water of reaction is formed.

Returning again to the preferred method of reaction and particularly from the standpoint of laboratory procedure employing a glass resin pot, when the reaction has proceeded as far as one can reasonably expect at a low temperature, for instance, after holding the reaction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C., for 4 or 5 hours, or at the most, up to 10-24 hours, We then complete the reaction by raising the temperature up to 150 C., or thereabouts as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of polyamine 0r formaldehyde. At a higher temperature we use a phaseseparating trap and subject the mixture to reflux condensation until the water of reaction and the water of solution of the formaldehyde is eliminated. We then permit the temperature to rise to somewhere about C., generally slightly above 100 C., and below C. by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined range. This period of heating and refluxing, after the water is eliminated, is continued until the reaction mass is homogeneous and then for one to three hours longer. The removal of the solvents is conducted in a conventional manner in the same way as the removal of solvents in resin manufacture as described in aforementioned U. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes we have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the secondary polyamine and 2 moles of formaldehyde. In some instances we have added a trace of caustic as an added catalyst but have found no particular advantage in this. In other cases we have used a slight excess of formaldehyde and, again, have not found any particular advantage in this. In other cases we have used a slight excess of amine and, again, have not found any particular advantage in so doing. Whenever feasible we have checked the completeness of reaction in the usual ways, including the amount of water of reaction, molecular weight, and particularly in some instances have checked whether or not the endproduct showed surface activity, particularly in a dilute acetic acid solution. The nitrogen content after removal ofdunreacted polyamine, if any is present, is another in ex.

In light of what has been said previously little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration Example 1b value for n which excludes the 2 external nuclei, i. e.,

the resin was largely a mixture having 3 nuclei and 4 nuclei, excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

23 882 grams of the resin identifiedas In preceding, were powdered and mixed with a considerably lesser weight of xylene, to wit, SOO grams. The mixture was As to the formulas of the above amines referred to as Amine A through Amine I, inclusive, see immediately following:

refluxed until solution was complete. Itwas then ad- Amine AHOC1HI CtHtOH justed to approximately 33 to 38 C., and 296 grams of symmetrical d1(hydroxyethyl)-ethylened1am1ne were add- H H ed. The mixture was stirred vigorously and formalde- A B H0O H hyde used was a 30% solution and the amount employed mm was 200 grams. It was added in a little over 3 hours. iHtN The mixture was stirred vigorously and kept within a H H temperature range of 33 to 48 C. for about 17 hours. Amine CFHOCH CIHOH At the end of this time it was refluxed using a phaseseparating trap and a small amount of aqueous distillate withdrawn from time to time. The presence of formalmm D H 11 dehyde was noted. Any unreacted formaldehyde seemed l e to disappear within about 3 hours or thereabouts. As CHTCHZ CHPCH soon as the odor of formaldehyde was no longer par- H -Cg HCNHCHCHz-NHCH HG-0H ticularly noticeable or detectable the phase-separating CHPCH, CHECK2 trap was set so as to eliminate part of the xylene was OH; H MC H OH) removed until the temperature reached approximately 2 1 150 C. or perhaps a little higher. The reaction mass Amme was kept at this temperature for a little over 4 hours and CH; CH; the reaction stopped. During this time any additional (3H3 water, which was probably water of reaction which had formed, was eliminated by means of the trap. The reits: iii j gg s gg sidual xylene was permitted to stay in the cogeneric e 2 'CH0HCH NHCHCHOH mixture. A small amount of the sample was heated on Amme H HOCHOHNHT(|JH' a water bath to remove the excess xylene. The residual HOCHICH1NHCH material was dark red in color and had the consistency of a stlcky flu1d or tacky resln. The overall time for Amine I CH3NHCH: reaction was somewhat under 30 hours. In other examples it varied from 24 to more than 36 hours. The GHNHCHTOHOH time can be reduced by cutting the low temperature CHaNHCHz period to approximately 3 to 6 hours. Note that in r PA 7 Table IV following there are a large number of added examples illustrating the same procedure. In each case In .prepanpg oxyalkylated denvatllfcs of products of the initial mixture was stirred and held at a fairly low the kmd winch appear as examples m Part Three we temperature to C) for a period of several have found 1t particularly advantageous to use laboratory hours. Then refluxing was employed until the odor of equlpment.whlch pcrmlts connimous oxypropylauon and formaldehyde disappeared. After the odor of formaldc- W oxyethylanon' The oxyethylanqn Step of course the hyde disappeared the phase separating trap was employed same as the OXYPI'OPYIEII'IOH step insofar that two low boilto separate out all the water, both the solution and con- 19g liquid? are handled n each q T oxyauiyla densation' After all the Water had been separated enough tron step is carried out in a manner which is substantially xylene was taken out to have the final product reflux for con-venuonal for the oxyalkylatlon of Compunds.having scveral hours somewhere in the range of to lab1le hydrogen atoms, and for that reason a detailed de- C., or thereabouts. Usually the mixture yielded a clear Simptlon the procedure ls omltted. and the process will Solution y the time thfi bulk of thfl Water or an of slmply be illustrated by the following examples: the water, had been removed. Example 10 Note that as Polfltfid f p y, {1118 pr c ure 18 w The oxyalkylation-susceptible compound employed is illustrated by 24 examples in Table IV. the one previously described and designated as Example TABLE IV Stren tn 1' R fig. 11212311! Amt, Ammo used and amount form lde Solventused 608: Eff: d i i iil. grs. hyde soln. and amt. tem time, tem

and amt. hrs. 882 Amine A, 296 grams .L 307, g... Xylene500g. 21-24 24 1 i 2:22 81 g Xylene 480 g 20-23 27 22 441 Amine B 1763mm" 30Zi50 i 610 22-27 25 142 480 AmineB l'ifigrams 37 7 81 gm x l 20-25 28 M5 63 0, 1 g. y ene 425 g 23-27 34 150 S82 g. Xylene 500 g- 25-27 30 152 8 37%, 162 g Xylene 625 m- 23-26 as 141 633 30%, g. Xylene 315 g. 20-21 25 143 473 30%, 100 g. Xylene 535 g 23-24 25 511 30%, 100 g. Xylene 425 g 22-25 25 148 665 100 g.-. Xylene 450 g 20-21 25 158 441 30%, 100 g"- Xylene 525 g 21-25 28 152 480 37%, 81 g Xylene 400 g. 22-24 26 143 595 37%, 81 g Xylene 400 g 25-27 36 144 441 37%, 81 g. Xylene 500 5;... 26-27 34 141 37%, 81 g Xylene 400 g 21-23 25 153 4%) 37%, 81 g Xylene 400 g 20-22 28 29 37%, 81 g Xylene 500 g- 23-25 27 155 8 37%, 81 g. Xylene 400 g 20-21 34 13) 2g 37%, 81 g. Xylene 450 20-24 36 152 441 v 37%, 81 g Xylene 500 g 20-22 30 148 595 AmineI '172 grams g i 5 i 391 Amine .86 mm 30 731505111 Xylene300g 20-26 36 1b. Condensate 1b was in turn obtained from symmetrical di(hydroxyethyl) ethylene diamine, previously de scribed for convenience as Amine A, and the resin pre' viously identified as Example 1a. Reference to Table III shows that this particular resin is obtained from paratertiarybutylphenol and formaldehyde. 12.02 pounds of this resin condensate were dissolved in 5 pounds of solvent (xylene) along with one pound of finely powdered caustic soda as a catalyst. Adjustment was made in the autoclave to operate at a temperature of approximately 130 C. to 135 C., and at a pressure of about 15 to 20 pounds. In some subsequent examples pressures up to 35 pounds were employed.

The time regulator was set oxide in approximately 1% hours, and then continue stirring for 15 minutes longer. The reaction went readily and, as a matter of fact, the oxide was taken up almost so as to inject the ethylene .immediately. Indeed the reaction was complete in less than an hour. The speed of reaction, particularly at the low pressure, undoubtedly was due in a large measure to excellent agitation and also to the comparatively high concentration of catalyst. The amount of ethylene oxide introduced was equal in weight to the initial condensation product, to wit, 12.02 pounds. This represented a molal ratio of 27.3 moles of ethylene oxide per mole of condensate.

The theoretical molecular weight at the end of the reaction period was 2404. A comparatively small sample, less than 50 grams, was withdrawn merely for examination as far as solubility or emulsifying power was concerned and also for the purpose of making some tests on various oil field emulsions. The amount withdrawn was so small that no cognizance of this fact is included in the data, or subsequent data, or in in tabular form in subsequent Tables V and VI.

The size of the autoclave employed was 25 gallons. In innumerable comparable oxyalkylations we have withdrawn a substantial portion at the end of each step and continued oxyalkylation on a partial residual sample. This was not the case in this particular series. Certain examples were duplicated as herein after noted and subjected to oxyalkylation with a difierent oxide.

Example 20 Example 40 Example 50 The oxyethylation continued with the introduction of another 12.02 pounds of ethylene oxide. No more solvent was introduced but .3 pound caustic soda was added. The theoretical molecular weight at the end of the agitationperiod was 7212, and the molal ratio of oxide to resin condensate was 136.5 to 1. The time period, however, was slightly less than before, to wit, 2 hours. Operating temperature and pressure remained the same as in the previous example.

Example 6c The same procedure was followed as in the previous examples. The amount of oxide added was another 12.02 pounds, bringing the total oxide introduced to the data presented same as at the end of the prior stage (Example 1c),

about 12.02 pounds. The amount of oxide present in the initial step was 12.02 pounds, the amount of catalyst remained the same, to wit, one pound, and the amount of solvent remained the same. The amount of oxide added was another 12.02 pounds, all addition of oxide in these various stages being based on the addition of this particular amount. Thus, at the end of the oxyethylation step the amount of oxide added was a total of 24.04 pounds and the molal ratio of ethylene oxide to resin condensate was 54.7 to 1. The theoretical molecular weightwas 3606.

The maximum temperature during the operation was 130 C. to 135 C. The maximum pressure was in the range of 15 to 20 pounds. The time period was a little less than before, to wit, only 45 minutes.

Example 30 The oxyalkylation proceeded in the same manner described in Examples 10 and 2c. There was no added solvent and no added catalyst. The oxide added was 12.02 pounds and the total oxide at the end of the oxyethylation step was 36.06 pounds. The molal ratio of oxide to condensate was 82.0 to 1. Conditions as far as temperature, pressure and time were concerned were all the same as in Examples 1c and 2c. The :time period was one hour.

72.12 pounds. The temperature and pressure during this period were the same as before. There was-no added solvent. The time period was 3 hours.

Example 70 The same procedure was followed as in the previous six examples without the addition of more caustic or more solvent. The total amount of oxide introduced at the end of the period was 84.14 pounds. The theoretical molecular weight at the end of the oxyalkylation period was 9616. The time required for the oxyethylation was the same as in the previous step, to wit, 3 hours.

Example 8c This was the final oxyethylation in this particular series. There was no added solvent and no added catalyst. The total amount of oxide added at the end of this step was 96.16 pounds. The theoretical molecular weight was 10,818. The molal ratio of oxide to resin condensate was 218 to 1. Conditions as far as temperature and pressure were concerned were the same as in the previous examples and the time required for oxyethylation t was slightly longer than in the previous step, to wit,

4 hours.

The same procedure as described in the previous examples was employed in connection with a number of the other condensates described previously. All these data have been presented in tabular form in a series of four tables, Tables V and VI, VII and VIII.

In substantially every .case a 25-gal1on autoclave was employed, although in some instances the initial oxyethylation was started in a 15-gallon autoclave and then transferred to a 25-gallon autoclave. but happened to be a'matter of convenience only. The solvent used inall cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Tables V and VI, it will be noted that compounds lc through 40c were obtained by the use of ethylene oxide, whereas 410 through 800 were obtained by the use of propylene oxide alone.

Thus, in reference to Table V it is to be noted as follows: i

The example number of each compound is indicated in the first column.

This is immaterial The identity of the oxyalkylation-susceptible compound, to wit, the resin condensate, is indicated in the second column. s I Y The amount of condensate is shown in the third column.

Assuming that ethylene oxide alone is employed as happens to be the case in Examples 1c through 40c, the amount of oxide present in the oxyalkylation derivative is shown in column 4, although in the initial step since no oxide is present there is a blank. 7

When ethylene oxide is used exclusively the 5th column is blank.

The 6th column shows the amount of powdered caustic soda used as a catalyst, and the 7th column shows the amount of solvent employed.

The th column shows the theoretical molecular weight at the end of the oxyalkylation period.

The 8th column states the amount of condensate present in the reaction mass at the end of the period.

As pointed out previously, in this particular series the amount of reaction mass Withdrawn for examination was so small that it was ignored and for this reason the resin condensate in column'8 coincides with the figure in column 3.

Column 9 shows the amount of ethylene oxide employed in the reaction mass at the end of the particular period.

Column 10 can be ignored insofar that no propylene oxide was'employed.

Column 12 shows the amount of solvent at the end of the reaction period.

Column 13 shows the molal ratio of ethylene oxide to condensate.

Column 14 can be ignored for the reason that no pro pylene oxide was employed.

Referring now to Table VIII. It is to be noted that the first column refers to Examples 1c, 20, 30, etc.

The second column gives the maximum temperature employed during the oxyalkylation step and the third column gives the maximum pressure.

The fourth column gives the time period employed.

The last three columns show solubility tests by shaking a small amount of the compound, including the solvent present, with several volumes of water, xylene and kerosene. It sometimes happens that although xylene is comparatively small amounts will dissolve in the concentrated material, when the concentrated material in turn is diluted with xylene separation takes place.

Referring to Table VI, Examples 41c through 800 are the counterparts of Examples 10 through 400, except that the oxide employed is propylene oxide instead of ethylene oxide. Therefore, as explained previously, two columns are blank, to wit, columns 4 and 9.

Reference is now made to Table VH. It is to be noted these compounds are designated by d numbers, 1d, 2d, 3d, etc., through and including 32d. They are derived, in turn, from compounds in the c series, for example, 370, 40c, 46c, and 770. These compounds involve the use of both ethylene oxide and propylene oxide. Since compounds 10 through 400 were obtained by the use of ethylene oxide, it is obvious that those obtained from 370 and 400, involve the use of ethylene oxide first, and propylene oxide afterward. Inversely, those compounds obtained from 46c and 770 obviously come from a prior series in which propylene oxide was used first.

In the preparation of this series indicated by the small letter d, as 1d, 2d, 3d, etc., the initial c series such as 370, 40c, 46c, and 77c, were duplicated and the oxyalkylation stopped at the point designated instead of being carried further as may have been the case in the original oxyalkylation step. Then oxyalkylation proceeded by using the second oxide as indicated by the previous explanation, to wit, propylene oxide in 1d through 16d, and ethylene oxide in 17d through 3211, inclusive.

. In examining the table beginning with 1d, it will be noted that the initial product, i. e., 370, consisting of the reaction product involving 12.02 pounds of the resin condensate, 30.05 pounds of ethylene oxide, 1.0 pound of caustic soda, and 5.0 pounds of the solvent.

It is to be noted that reference to the catalyst in Table VII refers to the total amount of catalyst, i. e., the catalyst present from the first oxyalkylation step plus added catalyst, if any. The same is true in regard to the solvent. Reference to the solvent refers to the total solvent present, i. e., that from the first oxyalkylation step plus added solvent, if any. 7

In this series, it will be noted that the theoretical molecular weights are given prior to the oxyalkylation step and after the oxyalkylation step, although the value at the end of one step is the value at the beginning of the next step, except obviously at the very start the value depends on the theoretical molecular weight at the end of the initial oxyalkylation step; i. e., oxyethylation for 1d through 16d, and oxypropylation for 17d through 32d.

It will be noted also that under the molal ratio the values of both oxides to the resin condensate are included.

The data given in regard to the operating conditions islfiubstantially the same as before and appears in Table The products resulting from these procedures may contain modest amounts, or have small amounts, of the solvents as indicated by the figures in the tables. If desired the solvent may be removed by distillation, and particularly vacuum distillation. Such distillation also may remove traces or small amounts of uncombined oxide, if present and volatile under the conditions employed.

Obviously, in the use of ethylene oxide and propylene oxide in combination one need not first use one oxide and then the other, but one can mix the two oxides and thus obtain what may be termed an indifferent oxyalkylation, i. e., no attempt to selectively add one and then the other, or any other variant.

Needless to say, one could start with ethylene oxide and then use propylene oxide, and then go back to ethylene oxide; or, inversely, start with propylene oxide, then use ethylene oxide, and then go back to propylene oxide; or, one could use a combination in which butylene oxide is used along with either one ofthe two oxides just mentioned, or a combination of both of them.

The colors of the products usually vary from a reddish amber tint to a definitely red, and amber. The reason is primarily that no effort is made to obtain colorless resins initially and the resins themselves may be yellow, amber, or even dark amber. Condensation of a nitrogenous product invariably yields a darker product than the original resin and usually has a reddish color. The solvent employed, if xylene, adds nothing to the color but one may use a darker colored aromatic petroleum solvent. oxyalkylation generally tends to yield lighter colored products and the more oxide employed the lighter the color of the product. Products can be prepared in which the final color is a lighter amber with a reddish tint. Such products can be decolorized by the use of clays, bleaching chars, etc. As far as use in demulsification is concerned, or some other industrial uses, there is no justification for the cost of bleaching the product.

Generally speaking, the amount of alkaline catalyst present is comparatively small and it need not be removed. Since the products per se are alkaline due to the presence of a basic nitrogen, the removal of the alkaline catalyst is somewhat more difficult than ordinarily is the case for the reason that if one adds hydrochloric acid, for ex ample, to neutralize the alkalinity one may partially neutralize the basic nitrogen radical also. The preferred procedure is to ignore the presence of the alkali unless it is objectionable or else add a stoichiometric amount of concentrated hydrochloric acid equal to the caustic soda present.

TABLE VII Composition beforo Composition at end Molalratio Molec. Ex.No. wt.

-8 0-8" Ethl. Propl. Cata- 801- 0-8 Ethl. Pro 1. Cata- Sol- Ethyl. Propl. based cmpd., cmpd., oxid oxide, lyst, vent, ompd., oxide, oxi e, lyst, vent, oxide oxide on theex.No. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. tooxyto oxyoretical alkyl. alkyl. value qnsmpt n mnt cmpd. empd.

Oxyelkylatlon-susceptible.

TABLE VIII Max. Max. Solubility Ex. temp., pres., Time, No. "0. p.s hrs.

Water Xylene Kerosene -20 1% Insoluble 15-20 Emulsifiable... 15-20 Soluble .1 15-20 15-20 15-20 15-20 15-20 15-20 15-20 15-20 15-20 15-20 15-20 15-20 15-15 10-15 10-15 10-15 10-15 10-15 10-15 10-15 10-15 -20 20-20 -30 25-30 25-30 25-30 25-30 25-30 10-15 10-15 10-15 10-15 10-15 10-15 10-15 10-15 20-25 20-25 2 20-25 2 20-25 2% 20-25 3 20-25 3 20-25 4% 20-25 5 -35 2 Insoluble. 30-35 3 D0.

TABLE VIII-Continued Time Solubility lll'S.

Water Xylene Kerosene Soluble D0. Dispersible. Soluble.

o. Insoluble.

Do. Do. Do. Dispersible.

Do. Dispersible. lnsollslble.

PART 8 The resin condensates which are employed as intermediate reactants are strongly basic. Initial oxyalkylation of these products with a monoepoxide or diepoxide can be accomplished generally, at least in the initial stage, without the addition of the usual alkaline catalyst such as those described in connection with oxyalkylation employing monoepoxides in Part Seven immediately preceding. As a matter of fact, the procedure is substantially the same as using a non-volatile monoepoxide such as glycide or methylglycide. However, during progressive oxyalkylation with a monoepoxide it is usually necessary to use a catalyst as previously described and, thus, there may or may not be sufficient catalyst present for the reaction with the diepoxide. Reference to the catalyst present includes the residual catalyst remaining from the oxyalkylation step in which the monoepoxide was used.

Briefly stated then, employing polyepoxides in combination with a nonbasic reactant the usual catalysts include alkaline materials, such as caustic soda, caustic potash, sodium methylate, etc. Other catalysts may be acidic in nature and are of the kind illustrated by iron and tin chloride. Furthermore, insoluble castalysts such as clay or specially prepared mineral catalysts have been used. If for any reason the reaction does not proceed rapidly enough with the diglycidyl ether or other analogous reactant then a small amount of finely divided caustic soda or sodium methylate can be employed as a catalyst. The amount generally employed would be 1% or 2% It goes without saying that the reaction can take place in an inert solvent, i. e., one that is not oxalkylation-susceptible. Generally speaking, this is most conveniently an aromatic solvent such as Xylene or a higher boiling coal tar solvent, or else a similar high boiling aromatic solvent obtained from petroleum. One can employ an oxygenated solvent such as the diethylether of ethyleneglycol, or the diethylether of propyleneglycol, or similar ethers, either alone or in combination with a hydrocarbon solvent. The selection of the solvent depends in part on the subsequent use of the derivatives or reaction products. If the reaction products are to be rendered solvent-free and it is necessary that the solvent be readily removed as, for example, by the use of vacuum distillation, then xylene or an aromatic petroleum solvent will serve. If the product is going to be subjected to oxyalkylation subsequently, then the solvent should be one which is not oxyalkylation-susceptible. It is easy enough to select a suitable solvent if required in any instance but, everything else being equal, the solvent chosen should be the most economical one.

7 35 Example la The product was obtained by reaction between the diepoxide previously described as Diepoxide 3A and oxyalkylated resin condensate 2c. Oxalkylated condensate 20 has been described in previous Part Seven and was obtained by the oxyethylation of condensate 1b. The preparation of condensate 1b was described in Part Six, preceding. Details have been included in regard to: both steps. Condensate 1b in turn, was obtained from symmetrical di(hydroxyethyl) ethylenediamine and has been described as amine A. The resin employed was resin 2a, which in turn, was obtained from para-tertiarybutylphenol and formaldehyde.

In any event, 361 grams of the oxyalkylated resin condensate previously identified as 20 were dissolved in .approximately an equal weight of xylene. About 3.5 grams of sodium methylate were added as a catalyst so the total amount of catalyst present, including residual catalyst from the prior oxyalkylation, was about 3.8 grams. 17 grams of diepoxide 3A were mixed with an equal Weight of xylene. The initial addition of the diepoxide solution was made after raising the temperature of the reaction mass to about 104 C. The diepoxide was added slowly over a period of one hour. During this time the temperature was allowed to rise to about 125 C. The mixture was allowed to reflux at about 134 C. using a phaseseparating trap. A small amount of xylene was removed by means of a phase-separating trap so the refluxing'temperature rose gradually to about 155 C. The mixture was refluxed at this temperature for about 5 hours; At the end of this period the xylene which had been removed by means of the phase-separating trap was returned to the mixture. A small amount of material was withdrawn and the xylene evaporated on a hot plate in order to examine thephysical'properties: The material was an amber, or light reddish amber, viscous liquid. It was insoluble in water; it was insoluble in gluconic acid, but it wassoluble in xylene' and particularly in a mixture of.80% xylene and 20% methanol. However, if the materialrwas dissolved in an oxygenated solvent and then shaken with-5% gluconic acid it showed a definite tendency to disperse, suspend, or form a sol, and particularly in a xylene-methanol mixed solvent as previously described, with or without the further addition of a little acetone; 7

Generally speaking, the solubility of these derivatives is in line with expectations by merely examining the solubility of the preceding intermediates, to wit, the oxyalkylated resin condensates prior to treatment with the diepoxide. These materials, of course, vary from extremely water-soluble products due to substantial oxyethylation, to those which conversely are water-insoluble but Xylene-soluble or even kerosene-soluble due to high stage oxypropylation. Reactions with diepoxides or polyepoxides of the kind herein, described reduce the hydrophile properties and increase the hydrophobe properties, i. e., generally make the products more soluble in kerosene or a mixture of kerosene and xylene, or in xylene, but less soluble in water. Since this is a general rule which applies throughout, for sake of brevity future reference to solubility will be omitted.

The procedure employed, of course, is simple in light of what has been said previously and in effect is a procedure similar to that employed in the use of glycide or methylglycide as oxyalkylating agents. See, for example, Part 1 of U. S. Patent No. 2,602,062 dated July 1, 1952 to De Groote.

Various examples obtained in substantially the same manner are enumerated in the following tables:

TABLE IX Ex. Oxy Amt., Diep- Amt Catalyst Xy- Molar Time of Max. No. resin congrs. oxide g'rs. (N a0 CHz), lene, ratio reaction, temp., Color and physical state densate used grs. grs. hrs. O.

361 3A 17 3. 8 378 2:1 4 155 Reddtsh-amber resinous mass. 301 3A 8. 6 3. 1 310 2:1 4 160 Do. 267 3A 17 2. 8 284 2: 1 4 158 Do. 276 3A 8. 6 2. 8 285 2: 1 5 145 D0. 415 3A 8. 5 4. 2 424 2: 1 4 160 D0. 240 3A 17 2. 6 257 2:1 4 160 D0. 481 3A 17 5. 0 498 2:1 5 150 Do. 267 3A 8. 5 2. 8 276 2: 1 6 152 Do. 237 3A 17 2. 5 254 2:1 5 146 Do. 474 3A 8. 5 4. 8 483 2: 1 6 145 Do. 481 3A 17 5. 0 498 2: 1 5 145 Do. 270 3A 8. 5 2. 8 279 2: 1 4 152 D0. 421 3A 8. 5 4. 3 430 2:1 4 150 D0. 481 3A 8. 5 4. 9 490 2: 1 4 154 D0. 138 3A. 1. 7 1. 4 140 2:1 4 150 D0.

TABLE X Ex. Oxy. .Amt. Diep- Amt, Catalyst Xy- Molar Time 01' Max. N o. resin congrs. oxide grs. (N :10 0B1), Iene, ratio reaction, temp., Color and physical state densate used grs. grs. hrs. 0.

361 B1 27. 5 3. 9 389 2:1 4. 5 150 Reddish-amber resinous mass. 301 B1 13. 8 3. 2 315 2: 1 4. 5 150 D0. 267 B1 27. 5 3. 0 295 2: 1 4. 5 157 Do. 276 B1 13. 8 2. 9 290 2:1 4. 5 155 Do. 415 B1 13. 8 4. 3 429 2:1 5 Do. 240 B1 27. 5 2. 7 268 2: 1 4 152 D0. 481 B1 27. 5 5. 1 509 2: 1 5 D0. 267 B1 13. 8 2. 8 281 2:1 4 D0. 237 B1 27. 5 2. 7 265 2:1 4 156 D0. 474 B1 13. 8 4. 9 488 2:1 4. 5 150 Do. 481 B1 27. 6 5. 1 509 2:1 5 148 D0. 270 B1 13. 8 2. 8 284 2:1 5 146 D0. 421 B 1 13. 8 4. 4 435 2 1 5 145 Do. 481 B1 13. 8 5. 0 495 2: 1 5 147 D0. 138 B1 2. 8 1. 4 141 2:1 4 150 Do.

TABLE XI Prob. mol. Ex. N o. g g ggj weight of Amount of Amount of densate reaction product, grs. solvent product TABLE XII Prob. mol. Ex. No. 9, 2 ,33 ,5 2: weigltlit of Aroutnt of Amimnttot reae on pro uc grs. so ven densate product At times we have found a tendency for an insoluble mass to form or at least to obtain incipient cross-linking or gelling even when the molal ratio is in the order of 2 moles of resin to one of diepoxide. We have found this can be avoided by any one of the following procedures or their equivalent. Dilute the resin or the diepoxide, or both, with an inert solvent, such as xylene or the like. In some instances an oxygenated solvent, such as the diethylether of ethyleneglycol may be employed. Another procedure which is helpful is to reduce the amount of catalyst used, or reduce the temperature of reaction by adding a small amount of initially lower boiling solvent, such as benzene, or use benzene entirely. Also, we have found it desirable at times to use slightly less than apparently the theoretical amount of diepoxide, for instance, 90% to 95% instead of 100%. The reason for this fact may reside in the possibility that the molecular weight dimensions on either the resin molecule or the diepoxide molecule actually may vary from the true molecular weight by several percent.

The condensate can be depicted in a simplified form which, for convenience, may be shown thus:

(Amine)CH (Resin) CH (Amine) If such product is subjected to oxyalkylation reaction involves the phenolic hydroxyls of the resin structure and, thus, can be depicted in the following manner:

(Amine) CH (Oxyalkylated Resin CH (Amine) Following such simplification the reaction with a polyepoxide, and particularly a diepoxide, would be depicted thus:

(Amine) CHflOxyalkylatted Resin) OH2(Amine) 38 example, a product which may be indicated thus in light of what has been said previously:

[ (Amine) CH (Resin) 0xyalkylated(Amine) CHz(Resin) Likewise, it is obvious that the two difierent types of oxyalkylation-susceptible compounds may combine so as to give molecules which may be indicated thus:

I(Amine) CH( Oxyalkylated Resin) CHn (Amine) I l (Amine) (lfiflOxyalkylated Resin) CHi(Amine) Oxyalkylated(Am1ne) 0 Hz (Amine) L. J

I Oxyalkylated (Amine) CHz(Resiu) Oxyalkylated (Amine) 0 Hi (Amine) l l Actually, the product obtained by reaction with a diglycidyl ether could show considerably greater complexity due to the fact that, as previously pointed out, the condensate reaction probably does not yield a hundred percent condensate in absence of other byproducts. All this simply emphasizes one fact, to wit, that there is no suitable method of characterizing the final reaction product except in terms of method of manufacture.

PART 9 Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, Xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the dernulsifying agent of our process may be admixed with sates '39 one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable well-known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they may be used in a form which exhibits relatively' limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials of our invention when employed as demulsifying agents.

The materials of our invention, when employed as treating or demulsifying agents, are used in the conventional way, well known to the art, described, for example, in Patent 2,626,929, dated January 27, 1953, Part 3, and reference is made thereto for a description of conventional procedures of demulsifying, including batch, continuous, and down-the-hole demulsification, the process essentially involving introducing a small amount of demulsifier into a large amount of emulsion with adequate admixture with or without the application of heat, and allowing the mixture to stratify.

In many instances the oxylalkylated products herein specified as demulsifiers can be conveniently used without dilution. However, as previously noted, they may be diluted as desired with any suitable solvent. For instance, by mixing 75 parts by weight of an oxyalkylated derivative, for example, the product of Example 3e, with parts by weight of xylene and 10 parts by Weight of isopropyl alcohol, an excellent demulsifier is obtained. Selection of the solvent will vary, depending upon the solubility characteristics of the oxyalkylated product, and of course will be dictated in part by economic considerations, i. e., cost.

As noted above, the products herein described may be used not only in diluted form, but also may be used admixed with some other chemical demulsifier. A mixture which illustrates such combination is the following:

Oxyalkylated derivative, for example, the product of Example 32,

A cyclohexylamine salt of a lene monosulfonic acid, 24%

An ammonium salt of a polypropylated naphthalene monosulfonic acid, 24%

A sodium salt of oil-soluble mahogany petroleum sul fonic acid, 12%;

A high-boiling aromatic petroleum solvent, 15%;

Isopropyl alcohol, 5%.

The above proportions are all weight percents.

PART 10 The products, compounds, or the like, herein described can be employed for various purposes and particularly for the resolution of petroleum emulsions of the water-inoil type as described in detail in Part Nine, preceding.

Such products can be reacted with alkylene irnines, such as ethylene imine or propylene imine, to produce cation-active materials. Instead of an imine one may employ what is a somewhat equivalent material, to wit, a dialkylaminoepoxypropane of the structure polypropylated naphtha- RI HQCN wherein R and R" are alkyl groups.

reaction with a' polyepoxide 'alkylated products obtained in the manner describedin It is not necessary to point out that, after reaction with a reactant of the kind described which introduces a basic nitrogenatom, the-resultant product can be employed for the resolution of emulsions of the water-in-oil type as described in Part 5, preceding, and also for other purposes described hereinafter.

Referring now to the use of the products obtained by and certain specified oxy- Part Seven, preceding, it is to be noted-that in addition to their use in the resolution of petroleum emulsions they may be used as emulsifying agents for oils, fats, and waxes, as ingredients in insecticide compositions, or as detergents and wetting agents in the laundering, scouring, drying, tanning and mordanting industries. They may also be used for preparing boring or metal-cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes.

Not only do these oxyalkylated derivatives have utility as such but they can serve as initial materials for more complicated reactions of the kind ordinarily requiring a hydroxyl radical. This includes esterification, etherization, etc.

The oxyalkylated derivatives may be used as valuable additives to lubricating oils, both those derived from petroleum and synthetic lubricating oils. Also, they can be used as additives to hydraulic brake fluids of the aqueous and non-aqueous types. They may be used in connection with other processes where they are injected into an oil or gas well for purpose of removing a mud sheath, increasing the ultimate flow of fluid from the surrounding strata, and particularly in secondary recovery operations using aqueous flood waters. These derivatives also are suitable for use in dry cleaners soaps.

More specifically, such products, depending on the nature of the initial resin, the particular monoepoxide selected and the ratio of monoepoxide to resin, together with the particular polyepoxide employed, result in a variety of materials which are useful as wetting agents or surface tension reducing agents; as detergents, emulsifiers or dispersing agents; as additives for lubricants, both of the natural petroleum type and the synthetic type, as additives in the flotation of ores, and at times as aids in chemical reactions insofar that demulsification is produced between the insoluble reactants. Furthermore, such products can be used for a variety of other purposes, including use as corrosion inhibitors, defoamers, asphalt additives, and at times even in the resolution of oil-inwater emulsions. They serve at times as mutual solvents promoting a homogeneous system from two otherwise insoluble phases.

The products herein described can be reacted with polycarboxy acids, such as phthalic acid or anhydride, maleic acid or anhydride, diglycolic acid, and various tricarboxy and tetracarboxy acids so as to yield acylated derivatives, particularly if one employs one mole of the polycarboxy acid for each reactive hydroxy radical present in the final polyepoxide-treated product. Thus, one obtains a comparatively large molecule in which there is a plurality of carboxyl radicals. Such acidic fractional esters are suitable for the resolution of petroleum emulsions of the water-in-oil type as herein described.

Having thus described our invention what we claim as new and desire to secure by Letters Patent is:

l. A three-step manufacturing process involving (1) condensation; (2) oxyalkylation with a monoepoxide; and (3) oxyalkylation with a polyepoxide containing at least two 1,2-epoxy rings; said first manufacturing step being a method of (A) condensing (a) a fusible, non-oxygenated organic solvent-soluble, water-insoluble, phenolaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric 

1. A THREE-STEP MANUFACTURING PROCESS INVOLVING (1) CONDENSATION; (2) OXYALKYLATION WITH A MONOEPOXIDE; AND (3) OXYALKYLATION WITH THE POLYEPOXIDE CONTAINING AT LEAST TWO 1,2-EPOXY RINGS; SAID FIRST MANUFACTURING STEP BEING A METHOD OF (A) CONDENSING (A) A FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, PHENOLALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITYF SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 